KR20160134659A - Polyphenylene sulfide porous body and production method thereof, polyphenylene sulfide-thermoplastic resin block copolymer and production method thereof - Google Patents

Abstract

A polyphenylene sulfide porous body having on its surface a porous region containing a porous structure and a non-porous region having substantially no porous structure. Provided is a novel polyphenylene sulfide porous body having heat resistance and chemical resistance and eliminating the trade-off between mechanical properties and permeation performance.

Description

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide porous body and a process for producing the same, a polyphenylene sulfide-thermoplastic resin block copolymer, and a process for producing the same. BACKGROUND ART Polyphenylene sulfide-

TECHNICAL FIELD The present invention relates to a polyphenylene sulfide porous body, a process for producing the same, and a polyphenylene sulfide-thermoplastic resin block copolymer and a process for producing the same. The polyphenylene sulfide-thermoplastic resin block copolymer is excellent in heat resistance and chemical resistance, And an excellent polyphenylene sulfide porous body.

The porous body is used as a separation membrane, a battery separator, a low dielectric constant material, an adsorbent, a catalyst carrier, a filter, and the like. Among them, the separation membrane is preferably used for separating and concentrating useful substances in the production of process water in electronic industry, chemical industry, mechanical industry, manufacturing of beverage by seawater desalination, production of medicines, foods and cosmetics, It is used in a wide range of fields including the medical field. In recent years, it has been continuously used in the field of environmental energy such as recovery of carbon dioxide gas generated from fossil fuel. Further, since the membrane separation process does not involve the phase transition of a gas or the like from the liquid, it is attracting attention as a separation process with a small energy load as compared with distillation, etc., and is capable of withstanding a severe use environment such as high temperature and high pressure, The demand for this excellent separation membrane is increasing.

As a conventional separation membrane material, an organic membrane or an inorganic membrane is known. As the material of the organic membrane, an organic membrane such as cellulose acetate, polysulfone, polyethersulfone, polyacrylonitrile, polypropylene, polyamide, polyvinylidene fluoride . Conventional organic films have the advantages of high productivity as compared with inorganic films. However, there are few materials that can be combined with heat resistance, chemical resistance, and low cost, and their applications are limited.

[Prior Art Literature]

[Patent Literature]

On the other hand, examples of the material of the inorganic film include zeolite, ceramic, glass, metal and the like (for example, Non-Patent Document 1).

A porous film using a polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) having excellent heat resistance and chemical resistance has been proposed. For example, there is known a method of dissolving and removing at least one component polymer other than PPS from a polymer alloy containing PPS to obtain a PPS porous body (see, for example, Patent Documents 1 and 2 ).

Also disclosed is a method of using N-methylpyrrolidone, diethylene glycol, benzophenone or the like as a solvent for PPS and kneading and extruding it to make it porous (for example, Patent Documents 3 and 4). In these methods, since the dense layer in the inner wall of the hollow fiber membrane serves as the separating layer and the sponge-like structure adjacent thereto serves as the support layer, the separation performance and mechanical characteristics are high.

As a manufacturing method of a separate PPS porous body, a method of forming a microporous body by stretching PPS is disclosed (for example, Patent Documents 5 and 6).

On the other hand, a block copolymer comprising a PPS oligomer having a carboxyl group at the terminal of the PPS chain and a polyester is also known (for example, Patent Document 7).

(Patent Document 1) Japanese Patent Application Laid-Open No. 2010-254943

(Patent Document 2) Japanese Unexamined Patent Application Publication No. 2331818

(Patent Document 3) Japanese Unexamined Patent Publication (Kokai) No. 60-248202

(Patent Document 4) Japanese Patent Application Laid-Open No. 2014-189747

(Patent Document 5) JP-A-58-67733

(Patent Document 6) Japanese Patent Application Laid-Open (JP-A) No. 59-59917

(Patent Document 7) JP-A-4-311725

[Non-Patent Document]

(Non-Patent Document 1) Future Material Vol.10. No. 7, p. 18

The inorganic film described in the non-patent document 1 has a relatively high heat resistance and chemical resistance, but has a problem that the film area per unit volume is small because of difficulty in processing into a hollow fiber shape, the cost is high, and the film performance is not stable.

In the methods of Patent Documents 1 and 2, since uniform and fine pores are obtained, separation performance as a separation membrane is high, but there is a problem that the mechanical properties of the porous membrane are low because there is no supporting portion for maintaining the strength as a membrane.

In the methods of Patent Documents 3 and 4, separation performance and mechanical characteristics are high, but the inner surface is covered with a dense layer, so that the fluid permeability is low. Further, in these methods, the solvent for dissolving PPS is very limited, and further, only in a pressurized state and at a high temperature of 200 DEG C or more, it is impossible to dissolve only in a severe condition, and therefore there is a problem that the film formation is very difficult, there was.

PPS porous bodies produced by the stretching methods of Patent Documents 5 and 6 have pores as a whole. Therefore, if the pore diameter is increased to improve the permeability, the trade-off property There was a problem, and it was impossible to achieve both the transmission performance and the mechanical characteristics. In addition, the shape of the molded article including the porous body is limited to the one that can be adapted to a drawing process such as a fiber or a film.

The block copolymer in the method of Patent Document 7 has been studied for the purpose of imparting flexibility to PPS, and the study of obtaining a porous body by removing the polyester from the block copolymer is mentioned not. Further, even when the polyester is removed from the block copolymer, the PPS of the porous material has a low molecular weight, so that heat resistance and chemical resistance are low, and mechanical properties are also low.

As described above, the PPS porous body which maintains heat resistance and chemical resistance inherent to PPS and has both mechanical properties and permeability of fluid is not known at present. An object of the present invention is to provide a PPS porous body having high heat resistance and chemical resistance, and having both mechanical properties and permeability.

In order to solve the above problems, the polyphenylene sulfide porous material of the present invention has the following constitution. In other words,

A polyphenylene sulfide porous body having a porous region including a porous structure and a nonporous region substantially not having a porous structure on its surface.

The method for producing the polyphenylene sulfide-thermoplastic resin block copolymer of the present invention has the following constitution. In other words,

Thermoplastic resin block copolymer which reacts polyphenylene sulfide (A) having a reactive functional group at its terminal with a thermoplastic resin (B) and a bifunctional linking agent (C).

The polyphenylene sulfide-thermoplastic resin block copolymer of the present invention is a polyphenylene sulfide-thermoplastic resin block copolymer having a polyphenylene sulfide unit and a thermoplastic resin unit bonded via a linking group containing a secondary alcohol Resin block copolymer.

The method for producing the polyphenylene sulfide porous material of the present invention has the following constitution. In other words,

Is a process for producing a polyphenylene sulfide porous body from which a thermoplastic resin component is decomposed and removed from the polyphenylene sulfide-thermoplastic resin block copolymer or the polyphenylene sulfide-thermoplastic resin block copolymer obtained by the above production method.

In the polyphenylene sulfide porous body of the present invention, it is preferable that the average area ratio of the porous region on the surface is 10 to 80%.

In the polyphenylene sulfide porous body of the present invention, it is preferable that the non-porous region is continuous on the surface.

The polyphenylene sulfide porous material of the present invention preferably has a porosity of 10 to 80%.

The polyphenylene sulfide porous material of the present invention is preferably composed of polyphenylene sulfide having a number average molecular weight (Mn) of 6,000 to 100,000.

The method for producing a polyphenylene sulfide-thermoplastic resin block copolymer of the present invention is characterized in that the reactive functional group of the polyphenylene sulfide (A) is an amino group, a carboxyl group, a hydroxyl group, a mercapto group, an isocyanato group, An acid anhydride group, an epoxy group, and derivatives thereof.

In the process for producing the polyphenylene sulfide-thermoplastic resin block copolymer of the present invention, it is preferable that the bifunctional linking agent (C) is an epoxy resin.

In the method for producing the polyphenylene sulfide-thermoplastic resin block copolymer of the present invention, it is preferable that the epoxy resin contains a halogen atom.

In the method for producing the polyphenylene sulfide-thermoplastic resin block copolymer of the present invention, the number average molecular weight of the epoxy resin is preferably 300 or more.

In the process for producing the polyphenylene sulfide-thermoplastic resin block copolymer of the present invention, the epoxy equivalent of the epoxy resin is preferably 200 g / ep or more.

The polyphenylene sulfide-thermoplastic resin block copolymer of the present invention has a structure in which the polyphenylene sulfide unit and the linking group are selected from the group consisting of secondary amines, esters, ethers, sulfides, amides, and siloxanes It is preferable to interpose them.

In the polyphenylene sulfide-thermoplastic resin block copolymer of the present invention, it is preferable that the connecting group contains a halogen atom.

The polyphenylene sulfide-thermoplastic resin block copolymer of the present invention preferably has a number average molecular weight (Mn) of the polyphenylene sulfide unit of 6,000 or more and 100,000 or less.

The polyphenylene sulfide-thermoplastic resin block copolymer of the present invention preferably has a number average molecular weight (Mn) of 10,000 or more and 2,000,000 or less.

According to the present invention, it is possible to provide a polyphenylene sulfide porous body which is excellent in heat resistance and chemical resistance as well as in both mechanical properties and fluid permeability.

1 is a photograph of the surface of a PPS porous body of the present invention prepared in Example 1 at a magnification of 1,300 times with a scanning electron microscope.

Hereinafter, the present invention will be described in detail.

(1) PPS porous body

The PPS porous body according to the present invention has a porous region having a porous structure on its surface and a non-porous region having no porous structure.

Here, the porous region is a region in which a porous structure in which at least three or more adjacent openings are aggregated with a space distance of not more than 5 times the hole diameter in an image of a scanning electron microscope (SEM) Specifically, a region in which a plurality of holes exist as shown in Fig. 1 (1). The void space indicates the shortest straight line distance between the outer periphery of the pore and the outer periphery of the pore adjacent to the pore. The void means a void having a pore diameter of 10 nm or more and a depth of at least a pore diameter. The non-porous region having substantially no porous structure refers to a region other than the porous region as shown in Fig. 1B, i.e., a region in which the void spacing is five times or more different from each other.

The porous region has a function as a channel for filling or permeating a fluid such as gas or liquid from the outside or the inside to the outside of the PPS porous body. On the other hand, the non-porous region has a function as a support for improving mechanical strength such as tensile, compression, bending, etc. of the PPS porous body. Therefore, by making the PPS porous body having the porous region and the non-porous region on the surface, the mechanical strength and the permeation performance of the fluid can be made compatible.

In the present invention, when the average area ratio of the porous region is 10 to 80%, it is preferable because the mechanical property and the permeability of the fluid can be made compatible. The average area ratio of the porous regions is more preferably 20% or more, and still more preferably 30% or more. The average area ratio of the porous region is more preferably 75% or less, and still more preferably 70% or less. Here, the average area ratio of the porous region is defined as the area (S) of the porous region and the area (S ') of the entire surface in the image of the surface of the PPS porous body observed with a scanning electron microscope having a magnification of 1,300 times The area ratio of the porous region calculated by the following formula is measured at arbitrary ten points and the average value thereof is taken.

Area ratio (%) of the porous region = (S) / (S ') 100

Further, in the case of the porous body in which the pores are present in a uniform frequency on the surface, all of them are non-porous regions (average area ratio of porous regions is 0%) or all porous regions (average area ratio of porous regions is 100% Of the PPS porous body.

The reason why the mechanical properties are improved when the area ratio of the porous region is within the above range is presumed as follows. That is, in the porous body having a high average area ratio of the porous regions, when external forces such as tensile, compressive, and bending are applied, cracks are generated in the public branch portions, and as a starting point, the whole structure is easily broken . On the contrary, the porous body having a low average area ratio of the porous region has a function of keeping the structure of the entire PPS porous body as a non-porous region on the surface, so that the structure is hardly destroyed. Therefore, if the non-porous region is continuous on the surface, the mechanical strength is improved, which is preferable. Here, the fact that the non-porous region is continuous on the surface means that when the surface is observed with a scanning electron microscope or the like, a sea-island structure in which a non-porous region is a sea component and a porous region is an island component, Means a structure in which non-porous regions are continuous in one direction like a layer. The tensile strength is preferably 50 MPa or more.

The porosity of the PPS porous body of the present invention is preferably 10 to 80%. Here, the porosity means the volume fraction of the porous portion with respect to the volume of the PPS porous body, and can be obtained by the following expression.

The porosity (%) = {(apparent volume - actual volume) / apparent volume} × 100

Here, the apparent volume refers to the volume of the entire PPS porous body including the pores. The actual volume refers to the volume occupied by the resin component in the PPS porous body, and is obtained by the following expression.

Actual volume = (weight of PPS porous body) / (specific gravity of PPS)

When the porosity of the PPS porous body is in the above-mentioned preferable range, the pressure loss when the fluid permeates the porous body is reduced, and the permeation performance can be improved. In addition, it is possible to increase the efficiency of adsorption or desorption of a substance, or to increase the charging efficiency when the substance is combined with other materials. On the other hand, mechanical strength such as tensile, compression, bending, etc. is not impaired. The porosity is more preferably 20% or more, and more preferably 30% or more. The porosity is more preferably 70% or less, and still more preferably 65% or less.

In addition, since the PPS porous body produced by the stretching method has anisotropy in mechanical characteristics because it is oriented in a specific direction, the PPS porous body of the present invention has an isotropic structure, so that the mechanical characteristics are isotropically excellent.

The average pore diameter of the PPS porous body of the present invention is not particularly limited, but may be in the range of 0.01 to 1 mu m. Here, the average pore diameter was obtained by observing 10 arbitrary cross sections of the PPS porous body by the cross section polish method (CP method) with a scanning electron microscope having a magnification of 100,000 times, And the average value thereof is taken as the average pore diameter.

The PPS porous body of the present invention may contain subcomponents such as resin components and additives other than PPS. Here, the subcomponent may be simply mixed with PPS or chemically bonded to PPS. When a component containing a halogen atom as a subcomponent is contained, the flame retardancy of the PPS porous body is improved, and it is more preferable that the component contains a bromine atom. Those containing a halogen atom can be detected by, for example, energy dispersive X-ray spectroscopy (EDX). If fibrous fillers are included as the other subcomponent, the mechanical strength of the PPS porous body can be further improved, which is preferable.

The number average molecular weight (Mn) of the PPS of the PPS porous material of the present invention is preferably 6,000 or more, because heat resistance and chemical resistance inherent to PPS are exhibited and a porous material excellent in mechanical characteristics such as mechanical strength and durability is obtained. And more preferably 15,000 or more. The upper limit of the number average molecular weight is not particularly limited, but it is preferably 100,000 or less since the moldability is excellent. Here, the molecular weight of PPS is measured by gel permeation chromatography, which is a kind of size exclusion chromatography, and is calculated in terms of polystyrene. The above-mentioned number average molecular weight (Mn) means the number average molecular weight of PPS containing other constituent components when other constituent components such as a linking agent are connected to the PPS porous body.

The macroscopic shape of the PPS porous body is not particularly limited, and various shapes such as fiber, film, sheet, resin molded article, and powder can be employed. For example, when used as a separator, it is preferable to use it as a hollow fiber membrane or a sheet-like flat membrane. Particularly, if the hollow fiber membrane is used, the membrane area per module is more preferable.

Since the PPS porous body of the present invention has a porous structure on the surface, the permeability of the fluid is higher than that of the structure including only the non-porous region on the surface. Here, the permeation performance is the amount of permeation, that is, the permeation flow rate, when a fluid is permeated from one surface of the porous body per unit time to the other surface under a certain pressure.

(2) Method for producing PPS-thermoplastic resin block copolymer and method for producing PPS porous body

The PPS-thermoplastic resin block copolymer of the present invention is produced by reacting at least a polyphenylene sulfide (A) having a reactive functional group at its terminal, a thermoplastic resin (B) and a bifunctional linking agent (C) , And it is possible to produce the PPS porous body by removing the component of the thermoplastic resin (B) from the block copolymer.

The structure of PPS (A) is a prepolymer having a repeating structure of a phenylene sulfide unit represented by the following general formula (I) and having a reactive functional group at the terminal.

(M in the general formula (I) represents the number of repeating units of phenylenesulfide units in PPS units)

The reactive functional group at the PPS end refers to a functional group capable of forming a chemical bond by reacting with a linking agent. The reactive functional group at the PPS terminal is preferably a functional group selected from the group consisting of an amino group, a carboxyl group, a hydroxyl group, a mercapto group, an isocyanato group, a silanol group, an acid anhydride group, an epoxy group and derivatives thereof. If the terminal structure of the PPS is such a reactive functional group, the reactivity with the linking agent is high, and the block copolymerization reaction of the PPS and the thermoplastic resin can proceed in a short time and at a high efficiency. Since the reactive functional group is present only at the end of the PPS, the sites that form a chemical bond with the linking agent are limited and the crosslinking reaction is inhibited, as compared with the case where the reactive functional group is present in the side chain of the PPS, A plastic resin block copolymer can be produced. Of the above-mentioned reactive functional groups, particularly preferred ones are functional groups selected from an amino group, a carboxyl group, a hydroxyl group and a mercapto group.

As a method of introducing a functional group at the end of the molecular chain, there can be mentioned a method of adding a sulfide compound (functional group-introducing agent) having a reactive functional group when the PPS is polymerized or a method of adding a sulfide compound having a reactive functional group And a method of reacting by adding an initiator). Specific examples of such sulfide compounds include bis (4-aminophenyl) sulfide, bis (4-carboxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide and oligomers thereof. The manufacturing method of PPS will be described in detail in (3).

In the present invention, the number average molecular weight (Mn) of PPS (A) used in the block copolymerization reaction is preferably 6,000 to 100,000. When the number average molecular weight is within this range, the number average molecular weight of PPS of the resulting PPS porous body can be obtained, and a PPS porous body having excellent heat resistance, chemical resistance, and mechanical characteristics can be obtained.

The thermoplastic resin (B) of the present invention is capable of forming a chemical bond by reacting with the bifunctional linking agent (C), and is not particularly limited as long as it is hydrolyzed, thermally decomposed, and oxidized and decomposed under the condition that PPS is not decomposed It is possible to employ various thermoplastic resins. Examples of the thermoplastic resin include polyesters, polycarbonates, polyamides, liquid crystal polymers, polyphenylene ethers, polyimides, polyetherimides, polysulfones, polyether sulfone, polyvinylidene fluoride, polytetrafluoroethylene, There may be mentioned polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylonitrile, polyvinyl alcohol, polyacetal, polyarylate, elastomer, polymethyl methacrylate, and epoxy resin. In the case of a thermoplastic resin having no reactive functional group reacting with a linking agent, a reactive functional group reactive with the bifunctional linking agent may be modified by chemical bonding to a thermoplastic resin before use.

As the block copolymerization reaction, it is preferable that the reaction is carried out at a high temperature of about 280 to 300 DEG C at which PPS is melted. Therefore, the thermoplastic resin (B) is preferably a resin having high thermal stability and easy decomposition and removal. Therefore, a polyester, a polycarbonate, a polyamide, a liquid crystal polymer and a polyarylate are preferable, and a polyester, a polycarbonate and a polyamide are more preferable from the viewpoint of cost. Among them, the aromatic polyester is more preferable since it has a relatively high heat resistance and can be easily hydrolyzed and removed by an aqueous alkali solution.

When a polyester is used as the thermoplastic resin (B), any polyester obtained by a polymerization reaction of a dicarboxylic acid or a dicarboxylic acid alkyl ester with a diol or a lactide may be used In particular, the use of polyethylene terephthalate or polybutylene terephthalate obtained by using ethylene glycol or 1,4-butanediol with terephthalic acid or its dimethyl ester is preferable because a PPS porous body can be produced at low cost.

When a polycarbonate is used as the thermoplastic resin (B), a phosgene method in which a dihydroxy diaryl compound is reacted with phosgene, or an ester in which a dihydroxy diaryl compound is reacted with a carbonic ester such as diphenyl carbonate Any of polycarbonates obtained by the exchange method, and polycarbonate prepared from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and phosgene.

When polyamide is used as thermoplastic resin (B), polylactam obtained by ring-opening polymerization of cyclic lactam, polyamide obtained by polycondensation of omega -aminocarboxylic acid, polycondensation of diamine and dicarboxylic acid Polyamides, semiaromatic polyamides, and the like, and examples thereof include nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, and nylon 6/612.

The melt viscosity of the PPS and the thermoplastic resin is not particularly limited, but generally, the closer the melt viscosity of the PPS to the thermoplastic resin, that is, the closer the melt viscosity ratio of the PPS to the thermoplastic resin is, the more the PPS and the thermoplastic resin It is preferable that the resin is apt to be subjected to differential oxidation when the resin is melt-kneaded, and the reaction rate of the block copolymerization reaction is improved. Here, the melt viscosity refers to the viscosity at the time of reaction and the shear rate.

In the production process of the present invention, a bifunctional linking agent (C) is used as a linking agent for block copolymerization of the PPS (A) and the thermoplastic resin (B). The term "linking agent" used in the present invention refers to a compound or resin having two reactive functional groups capable of forming a chemical bond by reacting with PPS or a thermoplastic resin and specific examples of the reactive functional group of the linking agent include an epoxy group, An isocyanato group, a silanol group, an alkoxysilane group, an amino group, a carboxyl group, an acid anhydride group, and a carbodiimide. Here, in the case of having three or more reactive functional groups in the molecule, the block copolymer may not be obtained by reacting with PPS or a thermoplastic resin and crosslinking. Therefore, in order to prepare a thermoplastic block copolymer, it is necessary to be a bifunctional linking agent. When the reactive functional group of the linking agent is an epoxy group, that is, the linking agent is an epoxy resin, it is possible to form a chemical bond by reacting with various functional groups such as amine, carboxylic acid, alcohol, aromatic alcohol, thiol, isocyanate, silanol, acid anhydride, And the reaction can proceed in a short time and at a high efficiency. The preferred form of the epoxy resin in the case of using an epoxy resin as a coupling agent is described in detail in (4).

The linking agent preferably contains a halogen atom in the molecule. Since a halogen atom has a larger atomic weight than a carbon atom, a nitrogen atom and an oxygen atom, the molecular weight of a linking agent is increased when a halogen atom is contained, and it is possible to suppress sublimation or evaporation when a PPS-thermoplastic resin block copolymer is produced It becomes. Further, the flame retardancy of the PPS-thermoplastic resin block copolymer can be improved by using the self-extinguishing property possessed by the halogen atom. The number of halogen atoms contained in the first molecule to be connected is not particularly limited, and it is possible to use a coupling agent containing at least one halogen atom in the molecule.

The heat resistance of the linking agent means that the thermal stability of the linking agent is high under a nitrogen atmosphere at 300 DEG C and 1 atm. Specifically, in a thermogravimetric (TG) apparatus, the temperature was raised from 30 DEG C to 300 DEG C with nitrogen flow at 30 DEG C / min, and then maintained at 300 DEG C for 10 minutes. Or more. Here, the weight retention ratio is calculated by the following equation. The weight retention ratio of 75% by weight or more is preferable because the heat resistance of the linking agent is higher and the reaction rate of the block copolymerization reaction is improved.

Weight retention ratio (% by weight) = (Weight of connecting agent after measurement (g)) / (Weight of connecting agent before measurement) × 100

When the PPS is reacted in the molten state, the reaction can be carried out at 280 to 300 ° C, or when the reaction is carried out in the solution state, at 200 to 250 ° C. Accordingly, when the heat resistance of the coupling agent is low, the ratio of the coupling agent that does not contribute to the reaction is increased due to sublimation, evaporation, and thermal decomposition of the coupling agent at a high temperature, and the reaction rate of the block copolymerization reaction is lowered. By having heat resistance of the linking agent, the reaction rate of the block copolymerization reaction can be improved.

Here, for example, when the PPS-thermoplastic resin block copolymer is produced, it can be produced under the non-catalytic condition, but the reaction can also be carried out in the presence of the catalyst. When the catalyst is added, the reaction rate of the block copolymerization reaction is improved by directly reacting the PPS with the thermoplastic resin. Examples of the catalyst that can be used in the present production method include catalysts used in the production of polyester, and specifically, manganese, cobalt, and cobalt, which are used as catalysts for the esterification reaction in the production of polyester, Magnesium, manganese, calcium, cobalt, zinc, lithium, titanium and the like which are used in the transesterification reaction and furthermore compounds such as antimony, titanium, aluminum, tin and germanium And the like.

The PPS component and the thermoplastic resin component may be connected not only to each other via a linking agent but also to a terminal structure derived from a repeating unit of each component. A plurality of PPS units or thermoplastic resin units may be present in one molecule of the block copolymer. That is, it may be not only a diblock copolymer or a triblock copolymer but also a multiblock copolymer having a tetrablock or more.

The mixing ratio of the PPS (A), the thermoplastic resin (B) and the bifunctional linking agent (C) can be set appropriately, but the PPS is preferably 10 to 90% by weight based on the total weight of the PPS, the thermoplastic resin, , More preferably from 20 to 80% by weight. When the mixing ratio of PPS is within the preferable range, the reaction rate of the block copolymerization reaction tends to be high and the morphology tends to become uniform. The thermoplastic resin is preferably 10 to 95% by weight, more preferably 20 to 90% by weight based on the total weight. When the thermoplastic resin is within the above-mentioned preferable range, the thermoplastic resin is less likely to become a dispersed component (island component) when the PPS and the thermoplastic resin are subjected to the block copolymerization, and it becomes easy to remove the thermoplastic resin component and make it porous.

The mixing ratio of the coupling agent is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight based on the total weight. The mixing ratio of the linking agent is preferably determined appropriately from the number average molecular weight of the PPS or the thermoplastic resin, the number of functional groups in the molecular chain, and the like.

The order of addition of the linking agent is not particularly limited, and they may be mixed and reacted simultaneously with PPS and thermoplastic resin. Alternatively, PPS and a linking agent, or a thermoplastic resin and a linking agent may be mixed and reacted in advance, It is also possible to mix and react the resin or PPS. In addition, a coupling agent may be added after the PPS and the thermoplastic resin are mixed in advance.

The temperature at which the mixture containing PPS, the thermoplastic resin and the linking agent is heated and reacted can not be uniformly defined because it depends on the molecular weight of PPS, the kind and molecular weight of the thermoplastic resin, the type and molecular weight of the coupling agent, And the melting point of the thermoplastic resin is preferably at least the melting point, and specific examples thereof are preferably 290 DEG C or higher, and more preferably 295 DEG C or higher. The upper limit of the reaction temperature is 400 占 폚 or lower, preferably 380 占 폚 or lower, more preferably 350 占 폚 or lower, and still more preferably 320 占 폚 or lower. When the reaction temperature is within such a preferable range, thermal decomposition of PPS and thermoplastic resin can be suppressed during the reaction, and sublimation, evaporation and thermal decomposition of the coupling agent can be suppressed. Here, the temperature at which the PPS and the thermoplastic resin are melted can be measured by a differential scanning calorimeter (DSC).

The polymerization atmosphere in the process for producing the PPS-thermoplastic resin block copolymer of the present invention can be appropriately employed, for example, in an inert atmosphere such as nitrogen, helium or argon, or under a reduced pressure or a high pressure have.

In the block copolymerization reaction, an organic polar solvent may be contained in the reaction system. Herein, the organic polar solvent means a solvent in which at least a part of PPS, thermoplastic resin and linking agent can be dissolved at the reaction temperature, for example, 1-chloronaphthalene, N-methyl- 2-pyrrolidone, N-methyl-epsilon -caprolactam, diethylene glycol, benzophenone, diphenyl ether and the like. The reaction temperature when an organic polar solvent is used may be a temperature at which PPS or a thermoplastic resin dissolves, but is preferably 180 DEG C or higher, more preferably 200 DEG C or higher. The upper limit of the reaction temperature is not particularly limited, but is preferably 260 占 폚 or lower, more preferably 250 占 폚 or lower. If the upper limit of the above-mentioned preferable reaction temperature is not exceeded, the coupling agent is not decomposed and the boiling point of the solvent is not exceeded. When it is necessary to conduct the reaction in excess of the boiling point, the reaction may be carried out using a high-pressure vessel such as an autoclave.

To the PPS-thermoplastic resin block copolymer, various other additives may be further added within the range not impairing the object of the present invention. Examples of the other additives include inorganic fillers such as fibrous inorganic fillers, fibrous inorganic fillers, fibrous organic fillers, sizing agents, silane coupling agents, antiwear agents, release agents, coloring inhibitors, plasticizers, antioxidants, ultraviolet absorbers, heat stabilizers, lubricants, Antiblocking agents, coloring agents including dyes and pigments, flame retardants, flame retardant auxiliaries, foaming agents, antibacterial agents and the like. The addition of a fibrous filler is preferable because the mechanical strength of the PPS porous body can be improved.

The PPS-thermoplastic resin block copolymer can adopt various shapes such as resin molded articles, films, sheets, fibers, and powders. In the case of a fiber or a film, stretching is also possible.

The method of producing the PPS porous body may be any method as long as it can chemically decompose and remove the thermoplastic resin component from the PPS-thermoplastic resin block copolymer, and any method such as hydrolysis, thermal decomposition, and oxidative decomposition can be used . Among them, a method of removing by hydrolysis is preferably used.

When a polyester, polycarbonate or polyamide is used as the thermoplastic resin (B), the swelling of the matrix component by the solvent can be suppressed by the method of hydrolysis and removal by an acidic aqueous solution or an alkaline aqueous solution, The removal time of the thermoplastic resin component can be shortened. In the case of using a polyester or a polycarbonate, an alkaline aqueous solution is more preferable because it is highly efficient in hydrolysis and can be removed in a short time. When a polyamide is used, it is preferable to remove it with an acidic aqueous solution.

The kind of the alkaline aqueous solution is not particularly limited, but it is preferable to use a hydroxide of an alkali metal or a hydroxide of an alkaline earth metal. It is preferable to use sodium hydroxide or potassium hydroxide from the viewpoint of cost, ease of availability and balance of hydrolysis rate Do.

The concentration of the alkaline aqueous solution is preferably in the range of 0.10 to 10M. When the concentration of the alkaline aqueous solution is within the above-described preferable range, the time required for decomposition and removal can be reduced, while the viscosity of the aqueous solution becomes excessively high and the efficiency of decomposition and elimination is not lowered.

The temperature of the alkaline aqueous solution is preferably 60 to 120 DEG C from the viewpoint of the hydrolysis rate of the thermoplastic resin component. From the viewpoint of the removal efficiency, the treatment in the pressurized state and the stirring treatment of the aqueous solution are also preferable.

After removing the thermoplastic resin component, it is preferable to remove the treatment liquid remaining in an appropriate solvent. For example, in the case of using a treatment with an acid or an aqueous alkali solution, washing with ion-exchanged water after treatment and then drying desirable.

Since the thermoplastic resin component in the block copolymer is decomposed and removed to form the pores, and the PPS component is not decomposed to form the pores of the porous region and the nonporous region by carrying out the above-described process, the PPS A porous body can be produced.

(3) Production method of PPS (A)

As an example of the above-mentioned production method of PPS (A), there are a process (A1) for producing PPS (A) in which the cyclic PPS (a) is heated in the presence of a sulfide compound having a reactive functional group and at least a sulfiding agent, (A2) for producing PPS (A) for heating a mixture containing an aromatic compound, an organic polar solvent and a monohalogenated compound having a reactive functional group. Hereinafter, the production method of these PPS (A) will be described in detail.

(3-1) Production method (A1) of PPS (A)

As a first preferred production method of PPS (A), there is a method of heating cyclic PPS (a) in the presence of a sulfide compound having a reactive functional group.

The addition amount of the sulfide compound in the production method (A1) of the PPS (A) is preferably 0.01 to 25 mol%, more preferably 0.01 to 15 mol%, based on 1 mol of the phenylenesulfide structural unit of the cyclic PPS (a) , More preferably from 0.01 to 10 mol%, and particularly preferably from 0.01 to 5 mol%. When the addition amount of the sulfide compound is in the above-mentioned preferable range, the introduction of the reactive functional group into the obtained PPS becomes sufficient, and the molecular weight of the obtained PPS becomes low, and the raw material cost increases.

The heating temperature in the production of the PPS (A) by the production method (A1) is preferably a temperature at which the reaction mixture containing the cyclic PPS (a) and the sulfide compound having a reactive functional group is melted, Condition does not require an excessively long time to obtain PPS (A). The temperature at which the cyclic PPS (a) is melted can not be shown uniquely because it varies depending on the composition and molecular weight of the cyclic PPS (a) and the environment at the time of heating. For example, Can be analyzed by a differential scanning calorimeter to determine the melting temperature. The lower limit of the heating temperature is 180 deg. C or higher, preferably 200 deg. C or higher, more preferably 220 deg. C or higher, and still more preferably 240 deg. C or higher. When the lower limit of the heating temperature is within this preferable temperature range, the cyclic PPS (a) is melted and PPS (A) can be obtained in a short time. Further, an undesirable side reaction typified by a cross-linking reaction or a decomposition reaction between cyclic PPS, between PPS generated by heating, between PPS and cyclic PPS does not occur, and even if the characteristics of the obtained PPS (A) Do not. The upper limit of the heating temperature is 400 占 폚 or lower, preferably 360 占 폚 or lower, and more preferably 340 占 폚 or lower. If the upper limit of the heating temperature is below this temperature, there is a tendency that adverse effects on the properties of the PPS (A) obtained by the undesirable side reactions can be suppressed.

The reaction time varies depending on the content of the cyclic compound in the cyclic PPS (a) to be used, various characteristics such as the number of repeating units (i) and molecular weight, the kind of the sulfide compound to be used, Therefore, it is preferable to set the above-mentioned undesirable side reaction so as not to occur. The heating time is, for example, 0.01 to 100 hours, preferably 0.05 to 20 hours, more preferably 0.05 to 10 hours.

The heating of the cyclic PPS (a) in the presence of a sulfide compound having a reactive functional group can be carried out under conditions substantially free of a solvent. When the reaction is carried out under these conditions, the temperature can be raised in a short time and the reaction rate is high, so that PPS (A) tends to be easily obtained in a short time. Herein, the condition substantially containing no solvent means that the solvent is 10% by weight or less based on the cyclic PPS (a), and more preferably 3% by weight or less.

The polymerization reaction of PPS (A) can be carried out not only by a method using a conventional polymerization reaction apparatus, but also in a mold for producing a molded article, by using an extruder or a melt kneader, It is possible to employ a known method such as a batch method or a continuous method.

Further, the reaction is preferably carried out in a non-oxidizing atmosphere, and it is also preferable to carry out the reaction under reduced pressure. In addition, in the case of performing under reduced pressure conditions, it is preferable to set the atmosphere in the reaction system once to a non-oxidizing atmosphere and then to the reduced pressure. This makes it possible to suppress the occurrence of undesirable side reactions such as cross-linking reaction and decomposition reaction between cyclic PPS, between PPS produced by heating, between PPS and cyclic PPS, and the like. In addition, the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gaseous phase to which the cyclic PPS is contacted is 5% by volume or less, preferably 2% by volume or less, more preferably an atmosphere substantially containing no oxygen such as nitrogen, helium, Nitrogen atmosphere is preferable from the viewpoints of economical efficiency and ease of handling. Further, in the case of conducting under reduced pressure, the pressure is preferably 50 kPa or less, more preferably 20 kPa or less, and further preferably 10 kPa or less, in order to suppress undesirable side reactions such as crosslinking reaction. As the lower limit of the decompression condition, 0.1 or more can be exemplified and 0.2 or more is more preferable in order to suppress the volatilization of the cyclic compound having a low molecular weight contained in the cyclic PPS.

The reaction can also be carried out under pressurized conditions. In the case of carrying out under the pressurizing condition, it is preferable to set the atmosphere in the reaction system once to a non-oxidizing atmosphere and then to the pressurizing condition. The pressurization conditions indicate that the system for carrying out the reaction is higher than the atmospheric pressure, and the upper limit is not particularly limited, but from the viewpoint of ease of handling of the reaction apparatus, 0.2 MPa or less is preferable.

In the production method (A1), the introduction rate of the terminal reactive functional group of PPS is high, and the production method is capable of increasing the molecular weight. As a result, the yield in the block copolymerization reaction can be improved and the molecular weight of the block copolymer can be increased.

(3-2) Production method (A2) of PPS (A)

A second preferred production method of PPS (A) is a production method (A2) in which a mixture containing at least a sulphidizing agent, a dihalogenated aromatic compound, an organic polar solvent and a monohalogenated compound having a reactive functional group is heated.

The amount of the dihalogenated aromatic compound used in the production method (A2) is preferably from 0.8 mol or more to less than 1.5 mol, more preferably from 1.5 mol or less, per mol of the sulfiding agent, from the viewpoints of suppressing decomposition and efficiently obtaining PPS having a viscosity suitable for processing More preferably from 0.9 to less than 1.05 mol, based on the total amount of the catalyst component. When the amount of the dihalogenated aromatic compound is in the above-mentioned preferable range, decomposition of the dihalogenated aromatic compound can be suppressed, and the molecular weight of the PPS (A) is not lowered, so that sufficient mechanical properties are exhibited.

In the production method (A2), the amount of the organic polar solvent to be used as the polymerization solvent for the PPS is not particularly limited, but from the viewpoint of stable reactivity and economic efficiency, 2.5 mol or more and less than 5.5 mol, Mole to less than 5.0 moles, and more preferably from 2.5 to less than 4.5 moles.

In the production method (A2), a monohalogenated compound having a reactive functional group is added when producing PPS, but the amount of the monohalogenated compound used is preferably in the range of 0.01 to 10 mol% relative to 1 mol of the dihalogenated aromatic compound , More preferably in the range of 0.1 to 8 mol%, and still more preferably in the range of 1 to 5 mol%. When the amount of the monohalogenated compound used is within the above-mentioned preferable range, the introduction rate of the reactive terminal in the obtained PPS (A) is not lowered, and the molecular weight of the PPS is lowered and mechanical properties are not exhibited.

The total amount of the halogenated compound such as a dihalogenated aromatic compound or a monohalogenated compound is preferably within a specific range, and the total amount of the halogenated compound relative to 1 mole of the sulfiding agent is preferably 0.98 mol or more and less than 1.10 mol, More preferably not less than 1.0 mole and not more than 1.08 mole, and still more preferably not less than 1.03 mole and not more than 1.07 mole. When the total amount of the halogenated compound with respect to 1 mol of the sulfiding agent is in the above-mentioned preferable range, decomposition of the halogenated compound can be inhibited, and the molecular weight of the PPS (A) is not lowered.

When the PPS (A) is produced by the production method (A2), the addition timing of the monohalogenated compound is not particularly limited and may be added at any time during the dehydration step, polymerization initiation, and polymerization as described later , But the addition of the monohalogenated compound is preferably carried out at a time when the conversion of the dihalogenated aromatic compound is less than 80%, more preferably less than 70%. From this point of view, it is most preferable to add it at the beginning of the polymerization, that is, simultaneously with the dihalogenated aromatic compound, from the completion of the dewatering process to the polymerization initiation. In the case where the addition of the monohalogenated compound is carried out in the above preferable period, there is no need for a reflux polymerization apparatus in which the monohalogenated compound is not volatilized during the dehydration step and a pressurizing apparatus for adding the monomer in the middle (pressurized state) The consumption of the monohalogenated compound is not completed and the polymer does not remain in the polymerization system.

In the production method (A2), the sulfiding agent can be used in the form of a hydrate or an aqueous mixture. However, before the addition of the dihalogenated aromatic compound or the monohalogenated compound, the mixture containing the organic polar solvent and the sulfiding agent is heated It is preferable to carry out a dehydration process for removing an excessive amount of water from the system. The dewatering method is not particularly limited, but preferably an alkali metal hydrosulfide and an alkali metal hydroxide are added to an organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C, preferably from room temperature to 100 ° C , The temperature is elevated to at least 150 ° C, preferably 180 to 260 ° C under atmospheric pressure or reduced pressure, and the water is distilled off. Further, it is preferable that the water content in the system at the stage where the dehydration step is finished is 0.9 to 1.1 moles per mole of the feed additive. Here, the water content in the system is the amount obtained by subtracting the water amount removed from the system from the water amount input in the dewatering step.

In the production method (A2), a polymerization step is carried out in which a reactant prepared in the dehydration step described above is contacted with a dihalogenated aromatic compound or a monohalogenated compound in an organic polar solvent to carry out a polymerization reaction. At the start of the polymerization process, a sulfiding agent and a polyhalogenated aromatic compound are added to an organic polar solvent preferably in an inert gas atmosphere at a temperature of 100 to 220 캜, preferably 130 to 200 캜. The order of introduction of these raw materials may be unequal or simultaneous.

The polymerization reaction is preferably carried out in a temperature range of 200 ° C or more and less than 280 ° C. The reaction conditions are not particularly limited. For example, there is a method in which the reaction is continued at a constant rate of 245 DEG C or more and less than 280 DEG C for a fixed period of time, The temperature is raised from 245 DEG C to less than 280 DEG C and the reaction is continued for a predetermined time; a method in which the reaction is continued for a predetermined time at a temperature of 200 DEG C or more and less than 245 DEG C, particularly 230 DEG C or more and 245 DEG C or less; And the reaction is completed in a short time.

The above-mentioned polymerization reaction is preferably carried out in a non-oxidizing atmosphere, preferably in an atmosphere of an inert gas such as nitrogen, helium or argon, and particularly preferably in a nitrogen atmosphere from the viewpoints of economical efficiency and ease of handling Do. The reaction pressure in the polymerization reaction is not particularly limited because it can not be uniformly defined depending on the type and amount of the raw material and solvent used, the polymerization reaction temperature, and the like.

In the method for producing a block copolymer of the present invention, PPS (A) may be recovered from the polymerization reaction product obtained by the above-mentioned method and used for the block copolymerization reaction. The polymerization reaction product includes PPS and an organic polar solvent, and other components may include unreacted raw materials, water, and by-product salts. There is no particular limitation on the method for recovering PPS from such a reaction mixture. For example, after removing a part or the majority of the organic polar solvent by an operation such as distillation if necessary, the solubility to the PPS component is low, A method in which PPS (A) is recovered as a solid by contacting with a solvent which is miscible with a solvent and has a solubility to a by-product salt under heating, if necessary. The solvent having such properties is generally a solvent having a relatively high polarity. The solvent is not limited because the preferred solvent differs depending on the type of the organic polar solvent and the by-product salt used. For example, water, methanol, ethanol, propanol, isopropanol, There may be mentioned, for example, alcohols such as butanol, hexanol, ketones represented by acetone and methyl ethyl ketone, and acetic acid esters such as ethyl acetate and butyl acetate. From the viewpoint of availability and economical efficiency, water, methanol and acetone , And water is particularly preferable.

By performing the treatment with such a solvent, it is possible to reduce the amount of the organic polar solvent and the by-product salt contained in the PPS (A). Since PPS (A) precipitates as a solid component by this treatment, it can be recovered using a known solid-liquid separation method. Examples of the solid-liquid separation method include separation by filtration, centrifugation, decantation, and the like. These series of treatments can be repeated several times as necessary, whereby the amount of organic polar solvent or by-product salt contained in PPS (A) tends to be further reduced.

As a method of treatment with the above-mentioned solvent, there is a method of mixing a solvent and a polymerization reaction product, and if necessary, it may be stirred or heated appropriately. The temperature for the treatment with the solvent is not particularly limited, but is preferably 20 to 220 캜, more preferably 50 to 200 캜. Such a range is preferable because, for example, it is easy to remove the by-product salt and the treatment can be performed at a relatively low pressure. When water is used as the solvent, it is preferable that the water is distilled water or deionized water. However, it is preferable to use water such as formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid, acrylic acid, crotonic acid, benzoic acid, salicylic acid, It is also possible to use an aqueous solution containing an organic acid compound such as an alkali metal salt, an alkaline earth metal salt, an inorganic acid compound such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid or silicic acid and an ammonium ion. When the PPS (A) obtained after this treatment contains the solvent used for the treatment, it is also possible to remove the solvent by carrying out drying or the like if necessary.

(3-3) The cyclic PPS (a)

The cyclic PPS contained in the cyclic PPS (a) used in the production method (A1) of the PPS (A) has a repeating unit represented by the formula - (Ph-S) - (Ph is a phenylene group) And is preferably a cyclic compound represented by the following formula (II) containing not less than 80 mol% of the repeating unit. The cyclic PPS (a) contains at least 50% by weight, preferably 70% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more, of the cyclic PPS of the formula (II) .

The upper limit value of the weight fraction of the cyclic PPS contained in the cyclic PPS (a) is not particularly limited, but is preferably 98% by weight or less, and more preferably 95% by weight or less. Generally, the higher the weight fraction of the cyclic PPS in the cyclic PPS (a), the higher the molecular weight of the PPS obtained after heating. On the other hand, when the weight fraction of the cyclic PPS in the cyclic PPS (a) exceeds the above upper limit value, the temperature of melting and melting tends to increase.

The repeating number i in the general formula (II) is not particularly limited, but is preferably i = 4 to 50, more preferably i = 4 to 25, and more preferably i = 4 to 15 . As described later, it is preferable to conduct the dialysis to the PPS by heating the cyclic PPS at a temperature not lower than the temperature at which the cyclic PPS is melted, and if the number of repeats i is within the above-mentioned preferable range, the temperature for melting the cyclic PPS does not become excessively high, It is possible to perform the dialing to the PPS of the cyclic PPS at a lower temperature.

The cyclic PPS may be a single compound having a single repetition number or a mixture of cyclic compounds having different repetition numbers, but a mixture of cyclic compounds having different repetition numbers is more soluble than a single compound having a single repetition number The use of a mixture of cyclic compounds having different repeating numbers is preferable because the temperature tends to be lowered so that the temperature at the time of dialing to PPS can be lowered.

The components other than the cyclic PPS in the cyclic PPS (a) are preferably PPS oligomers. Here, the PPS oligomer is a linear homo oligomer or a co-oligomer containing repeating units of the formula - (Ph-S) - as a main structural unit, preferably containing at least 80 mol% of the repeating units. As the molecular weight of the PPS oligomer, those having a lower molecular weight than that of PPS can be exemplified. Specifically, the number average molecular weight is preferably less than 5,000.

(3-4) sulfide compound

The sulfide compound used in the production method (A1) of the PPS (A) is a sulfide compound having a reactive functional group represented by the following general formula (III).

Herein, X and Y in formula (III) are reactive functional groups selected from at least one of amino group, carboxyl group, hydroxyl group, mercapto group, isocyanato group, silanol group, acid anhydride group and epoxy group, An amino group, a carboxyl group, and a hydroxyl group. When only one of X and Y has a reactive functional group, the other functional group is not particularly limited, and examples thereof include a hydrogen group and a halogeno group. The number of repeating p in the sulfide compound represents an integer of 0 to 20. p is an integer of preferably 0 to 15, more preferably 0 to 10. When the number of repeating p is within the above-mentioned preferable range, the solubility with the cyclic PPS and the low viscosity property are not impaired. In the production method (A1) of PPS (A), a mixture of sulfide compounds having different repeating number p may also be used.

Specific examples of such sulfide compounds include bis (2-aminophenyl) sulfide, bis (3-aminophenyl) sulfide, bis (2-hydroxyphenyl) sulfide, bis (3-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide, bis , Bis (4-hydroxy-3-methylphenyl) sulfide, 5,5'-thiodicarboxylic acid, 2,2 ', 4,4'-tetrahydroxydiphenyl sulfide and the like. . Among them, bis (4-aminophenyl) sulfide, bis (4-carboxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfide and oligomers thereof are more preferably used from the viewpoints of reactivity and crystallinity. These sulfide compounds may be used singly or in combination of two or more.

(3-5) Sulfide Feeding Agent

The sulfiding agent used in the production method (A2) of PPS (A) is not particularly limited as long as it can introduce a sulfide bond into a di-halogenated aromatic compound, and examples thereof include alkali metal sulfides, alkali metal sulfides and hydrogen sulfides have.

Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more thereof. Of these, lithium sulfide and / or sodium sulfide are preferable, Is more preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides. Further, the aqueous mixture refers to an aqueous solution, or a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component. The generally available cheap alkali metal sulfides are hydrates or aqueous mixtures, so it is preferable to use alkali metal sulfides of this type.

Specific examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium sulfide, and mixtures of two or more thereof. Among them, lithium hydrosulfide and / Sodium sulfide is preferable, and sodium hydrosulfide is more preferably used.

Alkali metal sulfides prepared from alkali metal hydrosulfide and alkali metal hydroxide in the reaction system can also be used. An alkali metal sulfide prepared by bringing an alkali metal hydrosulfide into contact with an alkali metal hydroxide in advance may also be used. These alkali metal hydrosulfides and alkali metal hydroxides can be used in the form of hydrates or aqueous mixtures or in the form of anhydrides, and hydrates or aqueous mixtures are preferred from the standpoint of availability and cost.

Alkali metal hydroxides such as lithium hydroxide and sodium hydroxide and alkali metal sulfides produced in the reaction system from hydrogen sulfide can also be used. An alkali metal sulfide prepared by bringing hydrogen sulfide into contact with an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide in advance may also be used. Hydrogen sulfide can be used in any form of gas, liquid, or aqueous solution.

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide together with the sulfiding agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more thereof. Specific examples of the alkaline earth metal hydroxides include calcium hydroxide, Strontium, barium hydroxide, etc. Among them, sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time. The amount of the alkaline metal hydrosulfide to be used is preferably from 0.95 to 1.50 mol, 1.25 mol, and more preferably 1.005 mol to 1.200 mol. In the case where hydrogen sulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time. In this case, the amount of the alkali metal hydroxide to be used is 2.0 to 3.0 mol, preferably 2.01 to 2.50 mol, And preferably 2.04 to 2.40 moles.

(3-6) A dihalogenated aromatic compound

Examples of the dihalogenated aromatic compound used in the production method (A2) of the PPS (A) include p-dichlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dibromobenzene, Bromobenzene, and 1-bromo-3-chlorobenzene, and a halogenated benzene such as 1-methoxy-2,5-dichlorobenzene, 1-methyl- Halogenated aromatic compounds containing substituents other than halogen such as dichlorobenzene, 1,4-dimethyl-2,5-dichlorobenzene, 1,3-dimethyl-2,5-dichlorobenzene and 3,5- . Among them, a halogenated aromatic compound containing p-dihalogenated benzene represented by p-dichlorobenzene as a main component is preferable. Particularly preferably, it contains 80 to 100 mol%, more preferably 90 to 100 mol% of p-dichlorobenzene. It is also possible to use two or more different dihalogenated aromatic compounds in combination.

(3-7) Organic polar solvent

As the organic polar solvent used in the production method (A2) of the PPS (A), an organic amide solvent can be preferably exemplified. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and N-cyclohexyl- , Aprotic organic solvents such as 1,3-dimethyl-2-imidazolidinone, N, N-dimethylacetamide, N, N-dimethylformamide and hexamethylphosphoric triamide, Is preferably used since it has high stability of the reaction. Among these, N-methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone are preferable, and N-methyl-2-pyrrolidone is more preferably used.

(3-8) Monohalogenated compound

The monohalogenated compound used in the production method (A2) of the PPS (A) may be any monohalogenated compound having a reactive functional group W represented by the following general formula (IV), but it is preferable that the reactive functional group W is an amino group, It is preferable that the compound has a functional group selected from a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a hydroxyl group, a carboxyl group and a hydroxyl group.

(V in the formula (IV) represents halogen)

Specific examples of such monohalogenated compounds include 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, 2-amino-4-chlorobenzoic acid, 4-chloro-3-nitrobenzoic acid, Monohalogenated compounds such as carboxylic acid, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-chlorophenol, 3-chlorophenol and 4-chlorophenol. Of these, 4-chlorobenzoic acid, 4-chloroaniline and 4-chlorophenol can be more preferably exemplified from the viewpoints of reactivity at the time of polymerization and versatility. These monohalogenated compounds may be used alone or in combination of two or more.

(4) Epoxy resin

A preferred embodiment of the epoxy resin in the case of using a bifunctional epoxy resin as a bifunctional linking agent will be described in detail. In general, the term epoxy resin is used in two meanings as a cured product obtained by reacting a prepolymer and a prepolymer before curing with a composition containing a curing agent and other components, but the epoxy resin in the present invention means a Quot; refers to a prepolymer having an epoxy group before curing.

The epoxy resin can react with various nucleophilic agents to form a chemical bond. Examples of the nucleophilic agent include amines, carboxylic acids, alcohols, aromatic alcohols, thiols, isocyanates, silanol, and acid anhydrides. When the epoxy resin reacts with these nucleophilic agents, the epoxy group is opened to form a secondary alcohol.

The number average molecular weight of the epoxy resin is not particularly limited, but is preferably 300 or more, more preferably 500 or more, and even more preferably 700 or more, because heat resistance is required for the epoxy resin. The upper limit of the number average molecular weight is preferably 3,000 or less, and more preferably 2,000 or less. When the upper limit of the number average molecular weight is in the above preferable range, miscibility with PPS or polyester is lowered, and the proportion of the epoxy resin which does not contribute to the block copolymerization reaction is not increased. The number average molecular weight of the epoxy resin is a value calculated in terms of polystyrene by GPC analysis.

The epoxy resin of the present invention preferably contains a halogen atom in the molecule. Since the halogen atom has a larger atomic weight than that of the carbon atom, the nitrogen atom and the oxygen atom, the molecular weight of the epoxy resin is increased, so that sublimation or evaporation can be suppressed when the block copolymer is produced. Further, as compared with the epoxy resin having the same molecular weight, since the molecular chain of the epoxy resin containing a halogen atom is short, the reactivity with the reactive functional group of the PPS or the thermoplastic resin is improved and the reaction rate of the block copolymerization reaction is improved . Further, the flame retardancy of the PPS-thermoplastic resin block copolymer can be improved by using the self-extinguishing property possessed by the halogen atom. The number of halogen atoms contained in one molecule of the epoxy resin is not particularly limited, and it is possible to use an epoxy resin containing at least one halogen atom in the molecule.

The epoxy equivalent weight of the epoxy resin of the present invention can be appropriately set in accordance with the amount of the end equivalent of PPS or polyester to be reacted. Here, the epoxy equivalent refers to the mass of the resin containing one equivalent of an epoxy group, and the unit thereof is represented by g / ep. From the viewpoint that the heat resistance of the epoxy resin is lowered when the epoxy equivalent is too small, it is preferably 200 g / ep or more. The upper limit of the epoxy equivalent is preferably 3,000 g / ep or less. If the upper limit of the epoxy equivalent is in the above-mentioned preferable range, the viscosity of the resin becomes too high, and the miscibility with PPS or polyester is not lowered.

The epoxy resin used in the present invention is not particularly limited as long as it has heat resistance and bifunctionality, and examples thereof include glycidyl ether type, glycidyl ester type, and olefin oxidized type (alicyclic type). Examples of the glycidyl ether type epoxy resin include epoxy resins such as bisphenol A type, bisphenol F type, bisphenol S type, hydrogenated bisphenol A type, hydrogenated bisphenol F type, biphenyl type, naphthalene type, aliphatic divalent alcohols, Epoxy resin obtained by reacting epichlorohydrin or? -Methyl epichlorohydrin, a prepolymer obtained by polymerization thereof, and various isomers, alkyl, halogen substituents and the like. Examples of glycidyl ester type epoxy resins include epoxy resins obtained by reacting dicarboxylic acids such as phthalic acid, hexahydrophthalic acid, dimeric acid, epichlorohydrin or? -Methyl epichlorohydrin, prepolymers obtained by polymerizing them, and And various isomers, alkyl, halogen substituents and the like. Examples of the olefin-oxidizing epoxy resin include conjugated or non-conjugated straight-chain dienes, epoxidized polyolefins such as conjugated or noncondensed cyclic dienes, prepolymers obtained by polymerizing them, and various isomers, alkyl, halogen substituents and the like. Also, an epoxy-containing olefin-based copolymer containing an? -Olefin and an?,? - unsaturated carboxylic acid glycidyl ester as a copolymerization component may be used.

Specific examples of the epoxy resin include, for example, chlorinated bisphenol A diglycidyl ether, brominated bisphenol A diglycidyl ether, chlorinated bisphenol F diglycidyl ether, brominated bisphenol F diglycidyl ether, bisphenol A diglycidyl ether prepolymer, a chlorinated bisphenol A diglycidyl ether prepolymer, a brominated bisphenol A diglycidyl ether prepolymer, a chlorinated bisphenol F diglycidyl ether prepolymer, a brominated bisphenol F di Glycidyl ether prepolymer and the like can be suitably used.

From the viewpoint of heat resistance, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, bisphenol A diglycidyl ether prepolymer, brominated bisphenol A diglycidyl ether prepolymer and the like are used . Use of brominated bisphenol A diglycidyl ether or brominated bisphenol A diglycidyl ether prepolymer is more preferable because it exhibits the effect of improving the flame retardancy of the block copolymer. These epoxy resins may be used alone or in combination of two or more.

(5) Polyphenylene sulfide-thermoplastic resin block copolymer

When a bifunctional epoxy resin is used as the bifunctional linking agent, the PPS-thermoplastic resin block copolymer of the present invention can be produced by a method comprising the steps of: mixing the PPS unit represented by the following general formula (I) Thermoplastic PPS-thermoplastic resin block copolymer (hereinafter simply referred to as " epoxy-linked block copolymer ") bonded via a linking group containing a secondary alcohol is obtained. Here, the thermoplasticity of the block copolymer means that 30 kg of the copolymer is heated at 300 캜 for 30 seconds to melt and deform the block copolymer.

The linking group contained in the block copolymer of the epoxy linkage is characterized by containing a secondary alcohol. Here, the term "linking group" refers to a structure in which a PPS unit and a thermoplastic resin unit are connected to form a block copolymer of PPS and a thermoplastic resin, and can be represented by the following general formula (V).

In the general formula (V), the structure of R is not particularly limited and is a group of various alkylene groups, aryl groups and the like, and R may contain a substituent. When the structure of R includes a halogen atom, it is preferable because the flame retardancy of the block copolymer is improved.

In the case of a block copolymer of an epoxy linkage, a secondary alcohol is produced when an epoxy group reacts with a PPS or a thermoplastic resin to form an epoxy resin as a precursor. In addition, the inclusion of the secondary alcohol exerts the effect of improving the hydrophilicity of the block copolymer or improving the adhesiveness with additives. The presence of the secondary alcohol can be confirmed by analyzing by a method such as infrared spectroscopy (IR) or nuclear magnetic resonance (NMR).

In the block copolymer of the epoxy linkage, it is preferable that the PPS unit and the linking group are bonded via a structure selected from the group consisting of a secondary amine, an ester, an ether, a sulfide, an amide, and a siloxane. When the reactive functional group of the PPS (A) is an amino group, a carboxyl group, a hydroxyl group, a mercapto group, an isocyanato group, a silanol group, an acid anhydride group or an epoxy group, Lt; / RTI >

The reason why the PPS unit and the linking group are bonded via the structure selected from the group consisting of secondary amine, ester, ether, sulfide, amide and siloxane is that the PPS-thermoplastic resin block copolymer is subjected to infrared spectroscopy IR), nuclear magnetic resonance (NMR), mass spectrometry, energy dispersive X-ray spectroscopy (EDX), and the like.

In addition, the PPS unit and the thermoplastic resin unit may be connected not only to each other via the above-mentioned linking group but also to the terminal structures derived from repeating each unit directly. A plurality of PPS units or thermoplastic resin units may be present in one molecule of the block copolymer. That is, it may be not only a diblock copolymer or a triblock copolymer but also a multiblock copolymer having a tetrablock or more.

The number average molecular weight of the block copolymer of the epoxy linkage varies depending on the structure of the thermoplastic resin forming the block copolymer and therefore can not be defined uniformly. However, it may be 10,000 or more, preferably 15,000 or more , More preferably 20,000 or more. The upper limit thereof is 2,000,000 or less, preferably 1,000,000 or less, and more preferably 500,000 or less. When the number average molecular weight of the block copolymer is within the above range, the physical properties of the block copolymer are improved. The block copolymer of the present invention is also a preferable form showing the molecular weight distribution of the monopoly. The number average molecular weight here is a value calculated by gel permeation chromatography (GPC) in terms of polystyrene.

Example

Hereinafter, the present invention will be described in detail. The present invention is not limited to these examples.

A. Measurement of molecular weight

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the PPS were calculated in terms of polystyrene by gel permeation chromatography (GPC), which is one kind of size exclusion chromatography (SEC). Measurement conditions of GPC are described below.

Device: Senshu Kagaku SSC-7100

Column name: Senshu Kagaku GPC3506

Eluent: 1-Chloronaphthalene

Detector: differential refractive index detector

Column temperature: 210 占 폚

Preheating bath temperature: 250 ℃

Pump thermostat temperature: 50 ℃

Detector temperature: 210 ° C

Flow rate: 1.0 mL / min

Sample injection amount: 300 μL (slurry phase: about 0.2% by weight)

B. Analysis of extraction rate of polyester

The polyester was extracted with 1.00 g of the reaction product of the block copolymer by melt-pressing to form a film having a thickness of 100 탆 or less, followed by freeze-grinding to obtain a powder. Subsequently, 30 g of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) was added, and the mixture was refluxed for 3 hours using an oil bath at 50 DEG C to remove unreacted poly The esters were eluted in HFIP. After heating and stirring for 3 hours, filtration was performed using a membrane filter having an average mesh size of 0.45 占 퐉 to separate and recover the HFIP soluble component and the insoluble component. The insoluble component was vacuum-dried overnight at 80 캜. The weight of each dry solid thus obtained was measured, and the extraction ratio of polyester was calculated from the weight before and after extraction by the following formula.

(% By weight) = weight after blocking reaction (g) / weight before blocking reaction (g) × 100

C. Determination of alkali weight loss rate of polyester

The alkali reduction rate when hydrolyzing the PPS-polyester block copolymer with an aqueous alkali solution was calculated by the following formula.

(Weight% before alkali hydrolysis) - (Weight after alkaline hydrolysis (g)) / (Weight before alkali hydrolysis (g)) 占 100

D. Observation of scanning electron microscope

The surface and cross section of the press film were observed using a scanning electron microscope (Hitachi High Technologies S-5500) by sputtering with platinum palladium.

E. Measurement of film thickness

The average value of the cross-sectional thicknesses at arbitrary 10 points of the porous body observed with a scanning electron microscope was taken as the film thickness.

F. Measurement of average pore diameter

When 10 arbitrary cross sections of the PPS porous body formed by the cross section polish method (CP method) were observed with a scanning electron microscope having a magnification of 100,000 times, the diameters of the pores in each observation image were measured, The average value was taken as the average pore diameter.

G. Measurement of the porosity

A PPS porous body on a disk having a diameter of 20 mm and a thickness of 50 m was prepared and the porosity was calculated by the following equation.

The porosity (%) = {(apparent volume - actual volume) / apparent volume} × 100

Here, the apparent volume and the actual volume were calculated by the following equations.

Apparent volume (m 3) = area of cut film (m 2) x film thickness (m)

Actual volume (m 3) = weight of porous body (g) / specific gravity of material (g · m ^-3 )

H. Measurement of tensile strength

As a tensile strength measurement method, a tensile tensile tester (UTM-4L, manufactured by Toyo Baldwin) was used. A rectangular sample having a length of 50 mm and a width of 10 mm was cut out from the PPS porous body and the tensile strength was measured at a tensile speed of 300 mm / min in an atmosphere at 25 ° C and a humidity of 65%.

I. Measurement of permeate flow of water

The permeation flow rate of water was determined in accordance with the reduced pressure filtration test of JIS K 3831 (1990) by fixing the PPS porous body (40 mm in diameter, 50 탆 in thickness) on the sheet in a stainless steel cell for filtration under reduced pressure. Using 500 mL of ion-exchanged water as a test solution, the time when the entire amount of the ion-exchanged water passed through the cell was measured at a gauge pressure of -10 ㎪, and the flow rate of the ion-exchanged water was calculated. Here, the measurement was carried out three times with a separate PPS porous body produced from the same level, and the average value thereof was defined as the permeation flow rate of water in the PPS porous body.

J. Analysis of Weight Retention Rate of Epoxy Resin

The analysis of the weight retention rate of the epoxy resin was carried out at a temperature of 90 캜 / minute to 300 캜 using a TG-DTA apparatus manufactured by Seiko Instruments, and then maintained at 300 캜 for 10 minutes. Then, the weight after measurement was measured, and the weight retention ratio was calculated by the following formula.

Weight retention rate (% by weight) = Weight after measurement (g) / Weight before measurement (g) × 100

[Referential Example 1] Production of cyclic PPS

12.50 g (0.144 mol) of a 48 wt% aqueous solution prepared by using 14.03 g (0.120 mol) of a 48 wt% aqueous solution of sodium hydrosulfide and 96% sodium hydroxide was added to a stainless steel autoclave equipped with a stirrer, 61.0 g (6.20 mol) of 2-pyrrolidone (NMP) and 18.08 g (0.123 mol) of p-dichlorobenzene (p-DCB) were charged. The inside of the reaction vessel was thoroughly purged with nitrogen, and then sealed under nitrogen gas.

And the temperature was elevated from room temperature to 200 DEG C over a period of about 1 hour while stirring at a rotational speed of 400 rpm. At this stage, the pressure in the reaction vessel was 0.35 MPa as a gauge pressure. Subsequently, the temperature was raised from 200 ° C to 270 ° C over about 30 minutes. The pressure in the reaction vessel at this stage was 1.05 MPa as a gauge pressure. Maintained at 270 DEG C for 1 hour, quenched to near room temperature, and then the contents were recovered.

The obtained contents were analyzed by gas chromatography and high performance liquid chromatography. As a result, it was found that the consumption rate of p-DCB of the monomer was 93% and the rate of cyclic PPS formation was 18.5% when the sulfur components in the reaction mixture were all converted into cyclic PPS. .

Next, 500 g of the obtained contents was diluted with about 1,500 g of ion-exchanged water and then filtered through a glass filter having an average mesh size of 10 to 16 탆. The components remained on the filter were dispersed with about 300 g of ion-exchanged water, stirred at 70 캜 for 30 minutes, and the same filtration was repeated three times in total to obtain a white solid. This was subjected to vacuum drying overnight at 80 캜 to obtain a dry solid. The obtained dry solid was put into a cylindrical filter paper and subjected to Soxhlet extraction using chloroform as a solvent for about 5 hours to separate a low molecular weight component contained in the solid content.

After the extraction operation, the solid component remaining in the cylindrical filter paper was vacuum dried overnight at 70 캜 to obtain about 6.98 g of an off-white solid. As a result of the analysis, from the absorption spectrum in infrared spectroscopy, it was a compound containing a PPS structure and also had a weight average molecular weight of 6,300.

After removing the solvent with the extract obtained by extracting with chloroform, about 5 g of chloroform was added to prepare a slurry, which was added dropwise to about 300 g of methanol while stirring. The precipitate thus obtained was collected by filtration, and vacuum-dried at 70 DEG C for 5 hours to obtain 1.19 g of a white solid. This white powder was confirmed to be a compound containing phenylenesulfide units from the absorption spectrum in infrared spectroscopic analysis. From the molecular weight information by MALDI-TOF-MS, the mass spectral analysis of the components separated by high-performance liquid chromatography (apparatus: Hitachi M-1200H) revealed that the white powder had p- , And further contains about 98% by weight of a cyclic compound having 4 to 13 repeating units as a unit, and is a cyclic PPS mixture suitably used for producing PPS (A) in the present invention. As a result of GPC measurement, the cyclic PPS mixture was completely dissolved in 1-chloronaphthalene at room temperature and had a weight average molecular weight of 900. [

[Referential Example 2] Production method of amino group-terminated PPS

Powder obtained by mixing 0.80 g (2.0 mol%) of bis (4-aminophenyl) sulfide per 1 mol of the PPS unit into 20 g of the cyclic PPS mixture obtained by the method described in Reference Example 1 was introduced into a glass ampule , And the inside of the ampoule was replaced with nitrogen. The ampoule was placed in an electric furnace whose temperature was controlled at 320 DEG C, and after heating for 120 minutes, the ampoule was taken out and cooled to room temperature to obtain a black solid. The product was dedicated to 1-chloronaphthalene at 250 占 폚. As a result of HPLC measurement, it was found that the conversion rate of cyclic PPS to PPS was 97.0%.

As a result of the GPC measurement, it was confirmed that the peaks derived from the cyclic PPS and the peaks of the generated PPS were found. The number average molecular weight of the obtained PPS was 16,000, the weight average molecular weight was 26,000, and the degree of dispersion was 1.62. The content of amino groups per mol of the PPS structural unit was 0.6 mol%.

[Referential Example 3] Production of carboxyl-terminated PPS

A black solid was obtained in the same manner as in Reference Example 2 except that bis (4-carboxyphenyl) sulfide was used in an amount of 0.5 mol% and the reaction time was changed to 120 minutes. The product was dedicated to 1-chloronaphthalene at 250 占 폚. As a result of HPLC measurement, it was found that the conversion rate of cyclic PPS to PPS was 96.2%. As a result of the GPC measurement, it was confirmed that the peaks derived from the cyclic PPS and the peaks of the generated PPS were found. The number average molecular weight of the obtained PPS was 17,000, the weight average molecular weight was 35,000, and the dispersion degree was 2.06. The content of the carboxyl group per mol of the PPS structural unit was 0.37 mol%.

[Referential Example 4] Production method of polyethylene terephthalate

100 parts by weight of dimethyl terephthalate, 60 parts by weight of ethylene glycol, and 0.05 mmol of magnesium acetate in terms of magnesium atom in 100 g of the obtained polymer were melted at 150 DEG C under a nitrogen atmosphere and then heated to 240 DEG C over 4 hours while stirring. And the ester exchange reaction was carried out to obtain bis (hydroxyethyl) terephthalate (BHT).

BHT was put into a test tube and maintained at a melting state at 250 ° C. Then, 0.2 mmol of antimony trioxide in terms of antimony atom was added per 100 g of the obtained polymer, and 0.1 mmol of trimethyl phosphate in terms of phosphorus atom was added per 100 g of the obtained polymer. The reaction was initiated after 5 minutes had passed after each compound was added. The inside of the reactor was gradually heated from 250 DEG C to 290 DEG C over 60 minutes and the pressure was reduced from normal pressure to 40 Pa over 60 minutes and polymerization was carried out at 290 DEG C and 40 Pa for 200 minutes. After completion of the polymerization reaction, the melt was discharged into a strand shape, cooled, and immediately cut to obtain pellets of polyethylene terephthalate. The intrinsic viscosity of the obtained polyethylene terephthalate was measured and found to be 0.69 dL / g.

[Example 1]

50 parts by weight of an amino group-terminated PPS obtained by the method described in Reference Example 2, 50 parts by weight of polyethylene terephthalate obtained by the method described in Reference Example 4, and 50 parts by weight of an epoxy resin , 7 parts by weight of brominated bisphenol A diglycidyl ether (Sigma Aldrich, epoxy equivalents: 350 to 450, weight retention: 95.3% by weight) as a bifunctional epoxy resin was measured, sealed in a test tube, and then replaced with nitrogen. Subsequently, the test tube was placed in an oil bath at 300 캜, and the mixture was allowed to stand for 5 minutes to melt the resin, followed by stirring. Stirring was stopped 5 minutes after the start of stirring, and the test tube was quenched to recover the product.

As a result of the GPC measurement, the chromatogram of the product was confirmed to be single-ended, having a number average molecular weight of 42,000 and a weight average molecular weight of 83,000, and high molecular weight by the block copolymerization of PPS used in the reaction was confirmed. Further, the obtained PPS-polyethylene terephthalate block copolymer was freeze-pulverized and subjected to extraction treatment with 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). As a result, the unreacted The polyethylene terephthalate was 30% by weight based on the polyethylene terephthalate added.

Then, the obtained PPS-polyethylene terephthalate copolymer was melt-pressed to produce a film (thickness 50 탆). Subsequently, the polyethylene terephthalate was hydrolyzed and removed by immersing in a 7M sodium hydroxide aqueous solution at 80 DEG C for 4 hours, washed three times with ion-exchanged water, and vacuum-dried at 100 DEG C for 3 hours to obtain a PPS porous body. When the molecular weight of the PPS porous body was measured by GPC, the number average molecular weight was 16,000 and the weight average molecular weight was 26,000. In addition, the macroscopic shape before and after the hydrolysis treatment did not change, and the weight reduction ratio of the block copolymer by the hydrolysis treatment was 46% by weight.

When the surface and cross section of the PPS porous body were observed by a scanning electron microscope, all the porous structures were observed. When the surface was observed at a magnification of 1,300 times, both the porous region and the non-porous region were observed, and the average area ratio of the porous region to the entire visual field observed was 55%. The non-porous region was continuous in the observed image. The PPS porous body had an average pore diameter of 0.25 mu m and a porosity of 47%. Table 1 shows the tensile strength and permeate flow rate of the obtained PPS porous body. The tensile strength was high and the permeation flow rate of water was large.

[Example 2]

A block copolymer was obtained in the same manner as in Example 1 except that the carboxyl group-terminated PPS obtained by the method described in Reference Example 3 was used. As a result of GPC measurement, the chromatogram of the product was single-ended and had a number average molecular weight of 37,000 and a weight average molecular weight of 72,000. Further, the resultant block copolymer was subjected to extraction treatment with HFIP. As a result, unreacted polyethylene terephthalate contained in the block copolymer was 38% by weight based on the added polyethylene terephthalate. Next, hydrolysis was carried out in the same manner as in Example 1, and the macroscopic shape before and after the treatment was not changed. The weight reduction ratio of the block copolymer by the hydrolysis treatment was 38% by weight.

When the surface of the PPS porous body was observed at a magnification of 1,300 times with a scanning electron microscope, both the porous region and the nonporous region were observed, and the average area ratio of the porous region to the observed visual field was 52%. The non-porous region was continuous in the observed image. The PPS porous body had an average pore diameter of 0.22 mu m and a porosity of 48%. Table 1 shows the tensile strength and permeate flow rate of the obtained PPS porous body.

[Example 3]

A block copolymer was obtained in the same manner as in Example 1, except that 35 parts by weight of amino terminal PPS, 65 parts by weight of polyethylene terephthalate, and 7 parts by weight of brominated bisphenol A diglycidyl ether were used. Further, the resultant block copolymer was subjected to extraction treatment with HFIP. As a result, unreacted polyethylene terephthalate contained in the block copolymer was 43% by weight based on the added polyethylene terephthalate. Next, hydrolysis was carried out in the same manner as in Example 1, and the macroscopic morphology before and after the hydrolysis treatment was not changed. The weight reduction ratio of the block copolymer by the hydrolysis treatment was 48% by weight.

When the surface of the PPS porous body was observed at a magnification of 1,300 times with a scanning electron microscope, both the porous region and the nonporous region were observed, and the average area ratio of the porous region to the observed visual field was 58%. The non-porous region was continuous in the observed image. The PPS porous body had an average pore diameter of 0.38 mu m and a porosity of 62%. Table 1 shows the tensile strength and permeate flow rate of the obtained PPS porous body.

[Example 4]

A block copolymer was obtained in the same manner as in Example 1, except that 65 parts by weight of amino terminal PPS, 35 parts by weight of polyethylene terephthalate, and 7 parts by weight of brominated bisphenol A diglycidyl ether were used. The resultant block copolymer was subjected to extraction treatment with HFIP. As a result, the unreacted polyethylene terephthalate contained in the block copolymer was 26% by weight based on the added polyethylene terephthalate. Next, hydrolysis was carried out in the same manner as in Example 1, and the macroscopic shape before and after the hydrolysis treatment was not changed, and the weight reduction ratio of the block copolymer by the hydrolysis treatment was 27% by weight.

When the surface of the PPS porous body was observed at a magnification of 1,300 times with a scanning electron microscope, both the porous region and the nonporous region were observed, and the average area ratio of the porous region to the observed visual field was 41%. The non-porous region was continuous in the observed image. The PPS porous body had an average pore diameter of 0.20 mu m and a porosity of 39%. Table 1 shows the tensile strength and permeate flow rate of the obtained PPS porous body.

[Comparative Example 1]

50 parts by weight of a commercially available PPS (Dorealizer "Torelina (registered trademark) E2088") and the cyclic PPS oligomer prepared in Reference Example 1 were mixed, Was supplied to a melt-kneader HK-25D (manufactured by Parka Corporation), and a melt film formation was conducted at 300 占 폚. The drum temperature was adjusted to 60 占 폚 and the winding speed was adjusted to prepare a 150 占 퐉 thick PPS polymer / cyclic PPS oligomer mixture film. The obtained film was cut into a circle having a diameter of 5 cm and immersed in 100 ml of N-methyl-2-pyrrolidone at 100 占 폚 for 12 hours to dissolve and remove the cyclic PPS oligomer. Washed with 20 ml of N-methyl-2-pyrrolidone, repeatedly washed three times with ion-exchanged water, and vacuum-dried at 100 DEG C for 3 hours to prepare a PPS porous film. When the surface of the PPS porous body was observed at a magnification of 1,300 times with a scanning electron microscope, only a uniform porous region was observed, and substantially no porous region was not present. The PPS porous body had an average pore diameter of 0.002 탆 and a porosity of 50%. Table 1 shows the tensile strength and permeate flow rate of the obtained PPS porous body. The permeate flow rate of water was high, but the tensile strength was low.

[Comparative Example 2]

17 parts by weight of commercially available PPS (Doreeze "Torelina (registered trademark) E2088"), 10 parts by weight of diethylene glycol, 73 parts by weight of N-methyl-2-pyrrolidone And the mixture was melted under a pressure condition of 250 ° C. This solution was discharged at 235 DEG C using a slit-type nip, passed through air in 22 mm, and then introduced into a coagulating bath of 60 wt% NMP to obtain a PPS film.

When the surface of the PPS porous body was observed at a magnification of 1,300 times with a scanning electron microscope, no pores were observed on the surface. The PPS porous body had an average pore diameter of 6 占 퐉 and a porosity of 45%. Table 1 shows the tensile strength and permeate flow rate of the obtained PPS porous body. The tensile strength was high, but the permeate flux was small.

[Comparative Example 3]

A press film of a PPS / polyethylene terephthalate blend was produced in the same manner as in Example 1 except that no bifunctional epoxy resin was added, and alkali hydrolysis treatment was carried out. In the PPS-polyethylene terephthalate block copolymer before hydrolysis, PPS is a sea component, and polyethylene terephthalate is a component in which the weight ratio is 0% by weight in the alkali treatment, It is a sea structure which is an island component, and even after the alkali treatment, the polyethylene terephthalate was not decomposed and removed.

The surface of the press film after alkali treatment with a scanning electron microscope was observed at a magnification of 1,300 times, and no voids were observed on the surface and the cross section. Table 1 shows the tensile strength and permeate flow rate of the obtained PPS porous body.

The polyphenylene sulfide porous material of the present invention can be used in various fields as a functional material having excellent heat resistance, chemical resistance, mechanical properties, and permeability. For example, the present invention can be widely used for applications such as a separator, a battery separator, a bug filter, a lightweight structural member, a dialysis membrane, a catalyst carrier, a heat insulator, a thermal insulator, a buffer material, a sorbent material and a low dielectric constant material. In addition, it is also possible to make various performance compatible by combining with other materials.

1: porous region
2: Non-porous region

Claims (17)

A polyphenylene sulfide porous body having on its surface a porous region containing a porous structure and a nonporous region having substantially no porous structure. The polyphenylene sulfide porous body according to claim 1, wherein an average area ratio of the porous region on the surface is 10 to 80%. 3. The polyphenylene sulfide porous body according to claim 1 or 2, wherein the non-porous region is continuous on the surface. The polyphenylene sulfide porous material according to any one of claims 1 to 3, wherein the porosity is 10 to 80%. The polyphenylene sulfide porous material according to any one of claims 1 to 4, which is composed of polyphenylene sulfide having a number average molecular weight (Mn) of 6,000 to 100,000. A process for producing a polyphenylene sulfide-thermoplastic resin block copolymer comprising reacting at least a polyphenylene sulfide (A) having a reactive functional group at a terminal thereof, a thermoplastic resin (B) and a bifunctional linking agent (C). The positive resist composition according to claim 6, wherein the reactive functional group of the polyphenylene sulfide (A) is at least one compound selected from the group consisting of amino group, carboxyl group, hydroxyl group, mercapto group, isocyanato group, silanol group, acid anhydride group, A method for producing a polyphenylene sulfide-thermoplastic resin block copolymer, which is selected. The method for producing a polyphenylene sulfide-thermoplastic resin block copolymer according to claim 6 or 7, wherein the bifunctional linking agent (C) is an epoxy resin. The process for producing a polyphenylene sulfide-thermoplastic resin block copolymer according to any one of claims 6 to 8, wherein the bifunctional linking agent (C) comprises a halogen atom. The method for producing a polyphenylene sulfide-thermoplastic resin block copolymer according to claim 8 or 9, wherein the epoxy resin has a number average molecular weight of 300 or more. The process for producing a polyphenylene sulfide-thermoplastic resin block copolymer according to any one of claims 8 to 10, wherein the epoxy equivalent of the epoxy resin is 200 g / ep or more. A polyphenylene sulfide-thermoplastic resin block copolymer having a polyphenylene sulfide unit and a thermoplastic resin unit bonded via a linking group containing a secondary alcohol. The polyphenylene sulfide-based resin composition according to claim 12, wherein the polyphenylene sulfide unit and the linking group are bonded via a structure selected from the group consisting of a secondary amine, an ester, an ether, a sulfide, an amide and a siloxane, Thermoplastic resin block copolymer. The polyphenylene sulfide-thermoplastic resin block copolymer according to claim 12 or 13, wherein the connecting group comprises a halogen atom. 15. The polyphenylene sulfide-thermoplastic resin block copolymer according to any one of claims 12 to 14, wherein the polyphenylene sulfide unit has a number average molecular weight (Mn) of 6,000 or more and 100,000 or less. 16. The polyphenylene sulfide-thermoplastic resin block copolymer according to any one of claims 12 to 15, wherein the number average molecular weight (Mn) is in the range of 10,000 to 2,000,000. The polyphenylene sulfide-thermoplastic resin block copolymer according to any one of claims 12 to 16 or the polyphenylene sulfide-thermoplastic resin block obtained by the production method according to any one of claims 6 to 11 A method for producing a polyphenylene sulfide porous material from a block copolymer by decomposing and removing a thermoplastic resin component.

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